Determination of imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole in fruits and vegetables by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry

Imidacloprid, metalaxyl, myclobutanil, propham, and thiabendazole have been simultaneously determined in strawberries, oranges, potatoes, pears, and melons by matrix solid-phase dispersion (MSPD) followed by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) in positive-ion mode. The samples were homogenized with C8 bonded silica as MSPD sorbent, placed in a glass column, and eluted with dichloromethane. Chromatographic separation of the compounds was achieved on a reversed-phase LC column using a methanol-ammonium formate (50 mmol L(-1)) gradient as a mobile phase. Samples were screened by monitoring the protonated molecular ion at m/z 256 for imidacloprid, 280 for metalaxyl, 289 for myclobutanil, and 202 for thiabendazole, and the main fragment at m/z 138 for propham. Positive samples were confirmed by multiple-ion monitoring. The repeatability (<20%) and recovery (>57%) of the method were good, and limits of detection (<0.05 mg kg(-1)) were adequate.     

On Extensions of Dynamical Systems by Function Algebras

A kind of extensions of dynamical systems by function algebras, which are called tame extensions, was introduced in [5] and [6]. In this paper, we search for sufficient conditions under which tame extensions preserve recurrence, periodicity, almost periodicity, semisimplicity, etc. To this end we introduce and study a new (stronger) kind of recurrence, which may be of independent interest. We also provide some examples which show that our hypotheses cannot, in general, be relaxed.     

A simple approach for the regioselective synthesis of imidazo[1,2-a]pyrimidiones and pyrimido[1,2-a]pyrimidinones

Several imidazo and pyrimido[1,2-a]pyrimidinones of type 1 and 2 were synthesized through intramolecular cyclization of pyrimidines 9 or pyrimidinones 10 bearing a variety of β and γ-aminoalcohols at the 2-position. Ring closure of the pyrimidinones of type 10 under Mitsunobu conditions lead to mixtures of both bicyclic regioisomers 1 and 2. Treatment of pyrimidines of type 9 with H₂SO₄ provided an efficient and operationally simple one-pot hydrolysis-cyclization procedure for obtaining imidazo and pyrimido[1,2-a]pyrimidinones 1 in good yields as the sole regioisomeric bicyclic product.     

Synthesis and conformational analysis of new cyclobutane-fused nucleosides

[structure: see text]. A stereselective synthesis of 3-oxabicyclo[3.2.0]heptane nucleoside analogues, which were designed as conformational mimics of the anti-HIV agents 2',3'-didehydro-2',3'-dideoxythimidine (stavudine, d4T) and 2',3'-didehydro-2',3'-dideoxyadenosine (d4A), is described. The target compounds were prepared by condensation of a common intermediate bicyclic acetate, derived from a homochiral 2(5H)-furanone, with pyrimidine and purine bases under modified Vorbrüggen conditions. The conformational behavior of the synthesized nucleoside analogues was studied by NMR spectroscopy and X-ray crystallography.     

Multilinear isometries on spaces of vector-valued continuous functions

In this paper we study multilinear isometries defined on certain subspaces of vector-valued continuous functions. We provide conditions under which such maps can be properly represented. Our results contain all known results concerning linear and bilinear isometries defined between spaces of continuous functions. The key result is a vector-valued version of the additive Bishop’s Lemma, which we think has interest in itself.     

Codimension 1 linear isometries on function algebras

Let be a function algebra on a locally compact Hausdorff space. A linear isometry is said to be of codimension if the range of has codimension in . In this paper, we provide and study a classification of codimension 1 linear isometries on function algebras in general and on Douglas algebras in particular.

     

Photochemical [2 + 2] cycloaddition of acetylene to chiral 2(5H)-furanones

The [2 + 2] photocycloaddition of acetylene to chiral 2(5H)-furanones was investigated. The influence on the chemical yield and facial diastereoselectivity of the substituent at the stereogenic center and also the effect of a 4-methyl group were evaluated. A mechanistic proposal based on a simple theoretical conformational analysis is presented. Using a C(2)-symmetric bis(lactone) as the substrate, a diastereomeric excess higher than 98% was found.     

Indirect analysis of urea herbicides from environmental water using solid-phase microextraction

We described here a solid-phase microextraction procedure used to extract six urea pesticides — chlorsulfuron, fluometuron, isoproturon, linuron, metobromuron and monuron — from environmental samples. Two polydimethylsiloxanes and a polyacrylate fiber (PA) are compared. The extraction time, pH control, addition of NaCl to the water and the influence of organic matter such as humic acid on extraction efficiency were examined to achieve a sensitive method. Determination was carried out by gas chromatography with nitrogen–phosphorus detection. The proposed method requires the extraction of 2 ml of sample (pH 4, 14.3%, w/v, NaCl) for 60 min with the PA fiber. The limits of detection range from 0.04 for linuron to 0.1 μg/l for fluometuron and monuron and the relative standard deviations at the 1 μg/l level are between 15% and 9%. The apparent fiber–water distribution constants (K_fw) calculated in the proposed conditions were in the order of 10³. Phenylurea herbicides were indirectly determined in the form of their derived anilines and chlorsulfuron in the form of an aminotriazine as confirmed by gas chromatography–mass spectrometry. Natural waters were utilized to validate the final procedure. However, a unequivocal identification in unknown environmental samples should be done by LC–MS. The presence of dissolved organic matter such as humic acid produces losses during the extraction step. Adding sodium chloride to the sample compensates for this effect.     

Evaluation of solid-phase extraction and stir-bar sorptive extraction for the determination of fungicide residues at low-microg kg(-1) levels in grapes by liquid chromatography-mass spectrometry

A liquid chromatography-mass spectrometry method has been developed for determining bitertanol, carboxin, flutriafol, pyrimethanil, tebuconazole and triadimefon. The evaluation of both atmospheric pressure interfaces (API), atmospheric pressure chemical ionization (APCI) and electrospray (ESI) using positive and negative ionization modes, clearly shows that the studied pesticides are more sensitive using APCI in positive mode. Two procedures based on solid-phase extraction (SPE) and stir-bar sorptive extraction (SBSE) have been assessed for extracting these compounds in grape. The recoveries obtained by SPE in samples spiked at the limit of quantification (LOQ) level ranged from 60 to 100% with relative standard deviation (R.S.D.s) from 7 to 17%. With the SBSE the recoveries obtained from samples spiked at LOQ level were between 15 and 100% and the R.S.D.s between 10 and 19%. The LOQs of most compounds are better by SPE (0.003-0.01 mg kg(-1)) than by SBSE (0.01 mg kg(-1) for all fungicides). Although SPE provided higher recoveries, lower R.S.D.s, best LOQs and is more rapid to carry out compared with SBSE, this last one has some advantages such as lower organic solvent consumption, and cleaner extracts. Results obtained applying both techniques to real samples are analogous.